Study of toughening modification of poly（lactic acid）/talc blends with hyperbranched polycaprolactone

doi:10.19491/j.issn.1001-9278.2025.08.005

Abstract

Abstract:

Hyperbranched polycaprolactone （HPCL） was synthesized via ring⁃opening condensation polymerization of ε⁃caprolactone using 2，2⁃dihydroxymethylpropionic acid as the initiator and stannous octoate as the catalyst. The synthesized HPCL was characterized and subsequently incorporated into a poly（lactic acid）（PLA）/talc blend. The PLA/talc/HPCL blends were systematically evaluated using infrared spectroscopy， morphological analysis， thermal analysis， mechanical testing， and melt flow rate measurements. Results demonstrated a non⁃monotonic relationship between HPCL content and crystallinity， with the maximum crystallinity （25.14%） achieved at 4 phr HPCL loading. The HPCL addition significantly enhanced the blend's processability， exhibiting a 74.6% improvement in melt flow rate at 7 phr HPCL loading compared to the unmodified PLA/talc blend. Notably， the HPCL modification substantially improved the blend's toughness. With 7 phr HPCL， the blends revealed an increase in elongation at break by 65.27% and impact strength by 80.28% relative to the baseline PLA/talc system. These findings demonstrate HPCL's effectiveness as a multifunctional modifier for simultaneously enhancing the crystallinity， processability， and mechanical properties of PLA/talc blends.

Key words: hyperbranched polycaprolactone, poly（lactic acid）, crystallinity, toughening

CLC Number:

TQ321

ZHANG Yusen, TIE Rui, LI Ziming, LIAO Baosheng, GUO Runqi, JIN Yujuan, ZHANG Zhe, JIANG Suchen. Study of toughening modification of poly（lactic acid）/talc blends with hyperbranched polycaprolactone[J]. China Plastics, 2025, 39(8): 26-33.

Figures/Tables 8

References 28

[1]	Nofar M， Sacligil D， Carreau P J， et al.Poly （lactic acid） blends： Processing， properties and applications［J］. International Journal of Biological Macromolecules，2019， 125：307⁃360.
[2]	Rezvani Ghomi E， Fatemeh K， Saedi Ardahaei A， et al.The life cycle assessment for polylactic acid （PLA） to make it a low⁃carbon material［J］. Polymers，2021， 13（11）： 1854.
[3]	Saini P， Arora M， Kumar M. Poly（lactic acid） blends in biomedical applications［J］. Advanced Drug Delivery Reviews， 2016， 107：47⁃59.
[4]	丁燕，江驰，潘剑婷，等.无机填料增强增韧聚乳酸基生物可降解材料的研究进展［J］. 云南化工，2024， 51（06）： 18⁃21.
	DING Y， JIANG C， PAN J T，et al. Development of inorganic filler⁃enhanced and toughening of PLA⁃based biodegradable materials［J］. Yunnan chemical industry， 2024， 51 （06）： 18⁃21.
[5]	汶少华.聚乳酸生物可降解材料填料复合改性研究进展［J］. 广州化工，2017， 45（03）： 6⁃8.
	WEN S H.Research on composite modification of PLA biodegradable materials［J］. Guangzhou chemical industry， 2017， 45 （03）： 6⁃8.
[6]	De Santis F， Pantani R. Melt compounding of poly （lactic acid） and talc： Assessment of material behavior during processing and resulting crystallization［J］. Journal of Polymer Research，2015， 22（12）：126.
[7]	Petchwattana N， Covavisaruch S， Petthai S.Influence of talc particle size and content on crystallization behavior， mechanical properties and morphology of poly（lactic acid）［J］. Polymer Bulletin，2014， 71（8）： 1 947⁃1 959.
[8]	许鹏飞，潘宏伟，张会良，等. 聚乳酸共混增韧和耐热性能的研究［J］. 塑料科技， 2020， 48（05）： 54⁃59.
	XU P F， PAN H W， ZHANG H L，et al.Study on acid toughness and heat resistance［J］. Plastic Technology， 2020， 48 （05）： 54⁃59.
[9]	Khuenkeao T， Petchwattana N， Covavisaruch S.Thermal and mechanical properties of bioplastic poly（lactic acid） compounded with silicone rubber and talc［C］//31st International Conference of the Polymer⁃Processing⁃Society （PPS），South Korea，2016.
[10]	Huda M S， Drzal L T， Misra M，et al.A study on biocomposites from recycled newspaper fiber and poly（lactic acid）［J］. Industrial & Engineering Chemistry Research，2005， 44（15）： 5 593⁃5 601.
[11]	Han X L， Jin Y J， Huang J， et al.Highly toughening modification of hyperbranched polyester with environment⁃friendly caprolactone as end group on poly（3⁃hydroxybutyrate⁃co-3⁃hydroxyvalerate）［J］. Journal of Polymers and the Environment， 2022， 30（8）： 3 209⁃3 217.
[12]	Li S P， Yao Y.Synergistic improvement of epoxy composites with multi⁃walled carbon nanotubes and hyperbranched polymers［J］. Composites Part B⁃Engineering， 2019， 165：293⁃300.
[13]	Yang J P， Chen Z K， Yang G， et al.Simultaneous improvements in the cryogenic tensile strength， ductility and impact strength of epoxy resins by a hyperbranched polymer［J］. Polymer，2008， 49（13/14）： 3 168⁃3 175.
[14]	Yoon C S， Ji D S. The effects of blend composition and blending time on the ester interchange reaction and tensile properties of PLA/LPCL/HPCL blends［J］. Fibers and Polymers，2003， 4（2）： 59⁃65.
[15]	Choi J， Kwak S Y.Hyperbranched poly（ε⁃caprolactone） as a nonmigrating alternative plasticizer for phthalates in flexible PVC［J］. Environmental Science & Technology，2007， 41（10）： 3 763⁃3 768.
[16]	Li Y， Yu E， Yang X，et al.Multiarm hyperbranched polyester⁃b⁃Poly（ε⁃caprolactone）：Plasticization effect and migration resistance for PVC［J］. Journal of Vinyl & Additive Technology，2020， 26（1）： 35⁃42.
[17]	Park H， Choe Y.Enhancing toughness and impact strength of epoxy resins by using hyperbranched polymers［J］. International Journal of Polymer Science，2021：689.
[18]	Tie R， Huang Y S， Jin Y J， et al.Toughening modification of polylactic acid by long⁃chain hyperbranched polymers containing polycaprolactone end groups［J］. Journal of Polymers and the Environment，2022， 30（12）： 5 327⁃5 338.
[19]	李艳，符金玉，冯刚，等.超支化聚己内酯对环氧树脂的增韧作用［J］. 高分子材料科学与工程，2018， 34（01）： 41⁃44.
	LI Y， FU J Y， FENG G，et al.Toughening effect of hyperbranched polycaprolactone on epoxy resin［J］. Polymer Materials Science and Engineering， 2018， 34 （01）： 41⁃44.
[20]	胡晨曦，王宇韬，吕明福，等.滑石粉改性PBAT/PLA复合材料的制备及性能研究［J］. 塑料科技，2022， 50（07）： 44⁃48.
	HU C X， WANG Y T， LV M F，et al.Preparation and Properties of Talcum Modified PBAT/PLA Composites［J］. Plastics Science and Technology，2022， 50（07）： 44⁃48.
[21]	李艳.超支化聚己内酯的合成及其增韧作用研究［D］.河北大学，2017.
[22]	孙闯闯，丁建萍，魏志和，等.耐水解PLA/PBS/滑石粉复合材料的制备及性能［J］. 现代塑料加工应用，2024， 36（02）： 33⁃36.
	SUN C C， DING J P， WEI Z H，et al.Preparation and properties of PLA / PBS / talc composites［J］. Modern Plastic Processing Applications， 2024， 36 （02）： 33⁃36.
[23]	Qian S， Zhang H， Yao W，et al.Effects of bamboo cellulose nanowhisker content on the morphology， crystallization， mechanical， and thermal properties of PLA matrix biocomposites［J］. Composites Part B⁃Engineering， 2018， 133：203⁃209.
[24]	Chattopadhyay D K， Webster D C.Thermal stability and flame retardancy of polyurethanes［J］. Progress in Polymer Science，2009， 34（10）： 1 068⁃1 133.
[25]	Huang J W， Fang Y Q， Zhou S D， et al.Enhanced compatibility and toughness of poly（3⁃hydroxybutyrate⁃co-3⁃hydroxyvalerate）/polycaprolactone blends by ring⁃opening polymerization and hydrogen bonding of epoxy⁃terminated hyperbranched polyester［J］. Journal of Applied Polymer Science，2024：981.
[26]	Liu Q， Shyr T W， Tung C H， et al.Particular thermal properties of poly（3⁃hydroxybutyrate⁃co-3⁃hydroxyvalerate） oligomers［J］. Journal of Polymer Research， 2012， 19（1）：981.
[27]	吴悠，王博华，孙健健，等.端环氧基型超支化聚合物对PPC/PBS共混物的改性研究［J］. 中国塑料， 2021， 35（04）： 5⁃11.
	WU Y， WANG B H， SUN J J， et al.Modification of PPC/PBS blend by terminal epoxy⁃type hyperbranched polymer［J］. Chinese Plastic， 2021， 35 （04）： 5⁃11.
[28]	Guo M， Jin Y， Han X， et al.Simultaneously strengthening and toughening biodegradable polylactic acid/thermoplastic starch blends by compatibilizing with epoxy⁃terminated hyperbranched polyester［J］. Journal of Polymers and the Environment，2024， 32（7）： 3 025⁃3 038.

样品	T_c/℃	△H_c/ J·g^-1	T_m1/ ℃	T_m2/ ℃	△H_m/ J·g^-1	X_c/%
PLA	99.96	—	—	172.36	10.38	15.83
PLA/滑石粉	105.23	21.79	156.22	164.44	16.02	24.42
1份HPCL	104.82	22.50	156.29	164.70	15.71	23.95
2份HPCL	104.41	21.47	155.94	164.52	16.21	24.71
3份HPCL	104.48	21.85	155.91	164.46	16.41	25.02
4份HPCL	104.68	21.53	155.94	164.42	16.49	25.14
5份HPCL	104.10	21.35	155.89	164.50	15.72	23.97
7份HPCL	103.91	20.32	156.03	164.55	15.40	23.48
10份HPCL	102.57	19.21	156.25	165.01	14.54	22.17

样品	T_c/℃	△H_c/ J·g^-1	T_m1/ ℃	T_m2/ ℃	△H_m/ J·g^-1	X_c/%
PLA	99.96	—	—	172.36	10.38	15.83
PLA/滑石粉	105.23	21.79	156.22	164.44	16.02	24.42
1份HPCL	104.82	22.50	156.29	164.70	15.71	23.95
2份HPCL	104.41	21.47	155.94	164.52	16.21	24.71
3份HPCL	104.48	21.85	155.91	164.46	16.41	25.02
4份HPCL	104.68	21.53	155.94	164.42	16.49	25.14
5份HPCL	104.10	21.35	155.89	164.50	15.72	23.97
7份HPCL	103.91	20.32	156.03	164.55	15.40	23.48
10份HPCL	102.57	19.21	156.25	165.01	14.54	22.17

样品	T_{d5 %}/℃	T_{d10 %}/℃	T_dmax/℃
PLA	358.87	366.37	391.73
PLA/滑石粉	297.07	320.56	360.24
1份HPCL	307.99	324.83	360.84
2份HPCL	302.99	319.31	359.44
3份HPCL	290.97	310.66	360.07
4份HPCL	291.97	308.95	356.67
5份HPCL	292.64	309.62	353.53
7份HPCL	298.25	310.94	351.98
10份HPCL	297.13	309.32	332.59

样品	T_{d5 %}/℃	T_{d10 %}/℃	T_dmax/℃
PLA	358.87	366.37	391.73
PLA/滑石粉	297.07	320.56	360.24
1份HPCL	307.99	324.83	360.84
2份HPCL	302.99	319.31	359.44
3份HPCL	290.97	310.66	360.07
4份HPCL	291.97	308.95	356.67
5份HPCL	292.64	309.62	353.53
7份HPCL	298.25	310.94	351.98
10份HPCL	297.13	309.32	332.59